Cellulose fiber-reactive disazo or trisazo dyes having a triazine ring substituted by A(B-sulfatoethyl) sulfonylanilino group

ABSTRACT

Reactive azo dyes represented by the general formula (I) or (II): ##STR1## wherein M is a hydrogen atom or an alkali metal, R 1  is a hydrogen atom, a chlorine atom, a lower alkyl group, a lower alkoxy group, a nitro group or a carboxyl group, R 2  and R 8  are a lower alkyl group, a lower alkoxy group or a sulfonic acid group, R 3 , R 7  and R 9  are a hydrogen atom, a lower alkyl group, a lower alkoxy group, an acetylamino group or a sulfonic acid group, R 4  and R 5  are a hydrogen atom, a methyl group, a methoxy group or a sulfonic acid group, R 6  is a hydrogen atom, a lower alkyl group, a lower alkoxy group or a sulfonic acid group, Z 1  is a chlorine atom, a fluorine atom, an aliphatic or an aromatic amino residual group, a methoxy group or a phenoxy group, Z 2  is the same one as Z 1  when Z 3  is ##STR2## Z 2  is a chlorine atom or a fluorine atom when Z 3  is an aliphatic amino residual group, an aromatic amino residual group except ##STR3## a methoxy group or a phenoxy group, Z 3  is ##STR4## an aliphatic amino residual group, an aromatic amino residual group except ##STR5## a methoxy group, or a phenoxy group, m is 1, 2 or 3, m&#39; is 2 or 3, n is 0 or 1, and the benzene rings A, B and C may be naphthalene rings.

FIELD OF THE INVENTION

This invention relates to novel reactive azo dyes.

BACKGROUND OF THE INVENTION

Up to now, the dyeing of cellulose fiber was carried out with a reactivedye at pH 10 and over in the presence of an acid capturing agent such assodium carbonate, potassium carbonate, sodium hydroxide and the like andan electrolyte such as sodium chloride, sodium sulfate and the like at atemperature of about 100° C. and below.

However, since in recent years the demand for the mixed spinning ofcellulose with other fibers, especially polyester fiber, is increasing,it is necessary to employ dyes and dyeing conditions suitable forcellulose and polyester fibers respectively, for dyeing of suchcellulose/polyester mixed fiber (hereinafter merely referred to as c/pfiber). This is because the dye and dyeing conditions for polyesterfiber are considerably different from those for cellulose fiber. Thatis, it is necessary to use a disperse dye for the dyeing of polyesterfiber at a temperature of about 130° C.

If the c/p fiber above is dyed in the same process at once, for example,the dyeing has to be carried out by using two different dyes and bymeans of a combination of a reactive dye and a disperse dye, but it hassome problems. For example, in order to exhaust the cellulose fiber partfully with a reactive dye, the pH value has to be kept at 10 and over bythe addition of an acid capturing agent. However, the presence of theacid capturing agent accelerates the decomposition of the disperse dyeto give poor exhaustion of the polyester fiber part. On the other hand,a high temperature condition is required in order that the polyesterfiber part is exhausted by a disperse dye. However, the hydrolysis ofthe disperse dye is accelerated under the high pH value stated above andthe high temperature, and thus, exhaustion of the cellulose fiberbecomes extremely inferior. Accordingly, the two-bath method, that is,one of cellulose or polyester fiber is dyed first and then the other isdyed by another bath, has been generally employed for dyeing of c/pfiber.

SUMMARY OF THE INVENTION

The object of this invention is to provide novel reactive azo dyes beingable to dye cellulose fiber under the condition and pH value which areemployed for dyeing of polyester fiber with a disperse dye.

That is, this invention relates to reactive azo dyes represented by thegeneral formula (I) or (II): ##STR6## wherein M is a hydrogen atom or analkali metal, R¹ is a hydrogen atom, a chlorine atom, a lower alkylgroup, a lower alkoxy group, a nitro group or a carboxyl group, R² andR⁸ are a lower alkyl group, a lower alkoxy group or a sulfonic acidgroup, R³, R⁷ and R⁹ are a hydrogen atom, a lower alkyl group, a loweralkoxy group, an acetylamino group or a sulfonic acid group, R⁴ and R⁵are a hydrogen atom, a methyl group, a methoxy group or a sulfonic acidgroup, R⁶ is a hydrogen atom, a lower alkyl group, a lower alkoxy groupor a sulfonic acid group, Z¹ is a chlorine atom, a fluorine atom, analiphatic or aromatic amino residual group, a methoxy group or a phenoxygroup, Z² is the same one as Z¹ when Z³ is ##STR7## Z² is a chlorineatom or a fluorine atom when Z³ is an aliphatic amino residual group, anaromatic amino residual group except ##STR8## a methoxy group or aphenoxy group, Z³ is ##STR9## an aliphatic amino residual group, anaromatic amino residual group except ##STR10## a methoxy group or aphenoxy group, m is 1, 2 or 3, m' is 2 or 3, n is 0 or 1, the benzenerings A, B and C may be naphthalene rings.

DETAILED DESCRIPTION OF THE INVENTION

In the reactive azo dyes of this invention represented by the generalformula (I) or (II), a sodium and potassium can be employed as an alkalimetal represented by M. As lower alkyl and alkoxy groups represented byR¹, R², R³, R⁶, R⁷, R⁸ and R⁹, alkyl and alkoxy groups having 1 to 4carbon atoms can be illustrated. As aliphatic or aromatic amino residualgroups represented by Z¹, Z² and Z³, an amino group, an alkylamino grouphaving 1 to 4 carbon atoms, an ethanolamino group, a β-cyanoethylaminogroup, a β-sulfoethylamino group, a glycine residual group, an anilinogroup and an anilino group substituted with a sulfo group, a chlorineatom, a lower alkyl group, a lower alkoxy group, a nitro group and acarboxyl group can be illustrated.

The reactive azo dye represented by the general formula (I) stated abovecan be prepared by the following procedure: For example, the usualdiazotization and coupling can be carried out with the compoundrepresented by the general formulae (III) and (IV): ##STR11## to givethe monoazo compound represented by the general formula (V). ##STR12##

On the other hand, the compounds represented by the general formulae(VI), (VII) and (VIII): ##STR13## can be condensed each other in anaqueous medium in any order to prepare the compound represented by thegeneral formula (IX). ##STR14##

Then, the monoazo compound of the general formula (V) can be convertedto the diazonium compound by the usual diazotization, and the diazoniumcompound is coupled with the compound represented by the formula (IX) toobtain the reactive azo dyes of the general formula (I) stated above.

The reactive trisazo dyes represented by the general formula (II) statedabove involve two kinds of the compounds represented by the generalformulae (II-1) and (II-2). ##STR15## wherein X is a chlorine atom or afluorine atom, Y is an aliphatic amino residual group, an aromatic aminoresidual group except ##STR16## a methoxy group or a phenoxy group, andR⁴, R⁵, R⁶, R⁷, R⁸, R⁹, M Z¹, m' and n are the same meanings as definedhereinbefore.

The trisazo compound represented by the general formula (II-1) statedabove can be prepared by the following procedure: For example, the usualdiazotization and coupling can be carried out twice with the compoundsrepresented by the general formulae (X), (XI) and (XII): ##STR17## togive the disazo compound represented by the general formula (XIII).##STR18##

Then, the disazo compound of the general formula (XIII) stated above canbe converted to the diazonium compound in water-acetic acid medium bydiazotization, and then the diazonium compound obtained is coupled withthe compound represented by the general formula (IX) stated above toobtain the trisazo compound of the general formula (II-1) stated above.

Also, the trisazo compound represented by the general formula (II-2) canbe prepared by the following procedure: For example, the compoundsrepresented by the following formulae (XIV), (XV) and (XVI): ##STR19##can be condensed each other in an aqueous medium in any order to preparethe compound represented by the general formula (XVII): ##STR20##

Then, the disazo compound of the general formula (XIII) stated above canbe converted to the diazonium compound in water-acetic acid medium bydiazotization, and the diazonium compound obtained can be coupled withthe compound represented by the general formula (XVII) stated above toobtain the trisazo compound of the general formula (II-2) stated above.

As fibers which can be dyed with reactive azo dyes of this invention,cellulose fiber such as cotton, viscose rayon, cupra ammonium rayon andhemp, can be illustrated. Also, cellulose fiber in mixed cellulosefibers with polyester, triacetate, polyacrylonitrile, polyamido, wool,silk and the like can be excellently dyed.

In dyeing method for fibers using reactive azo dyes of this invention,dyeing can be carried out by adding a dyestuff which is needful fordyeing of fibers other than cellulose, e.g., a disperse dye and the likestated in Color Index (Third Edition), into the bath at the same time.

In case of dyeing of cellulose fibers with a reactive azo dye of thisinvention, for example, a bath can be prepared by adding a reactive azodye represented by the general formula (I) or (II), a buffer which isrequired to keep the bath at pH 5 to 10 (for example, in general, about0.5 to 5.0 g of an acid such as carbonic acid, phosphonic acid, citricacid and the like, a sodium salt or a potassium salt with these acid ora mixture thereof per liter), and if necessary, by adding an electrolyte(in general, about 1 to 150 g of sodium chloride, sodium sulfate and thelike per liter), and a cellulose fiber is put in the bath, and thendyeing can be carried out by heating the bath for 30 to 50 minutes attemperature of 100° to 150° C.

When mixed fiber and knitted goods made by spinning or knittingcellulose fiber with other fibers, for example, polyester fiber, aredyed, the cellulose and polyester fibers can be dyed at the same time byadding a reactive azo dye represented by the general formula (I) or (II)and a disperse dye stated in Color Index into the bath above accordingto one-bath one-process method.

Furthermore, in the case of dyeing the mixed fiber and knitted goodsabove, the one-bath two-process method heretofore in use, that is,either fiber is dyed and then the other fiber is dyed, may be applied todye cellulose and other fibers in each bath by combination of dyeingmethod using a reactive azo dye of this invention with dyeing method forother fibers other than cellulose.

The method of this invention is described in detail later by means ofexamples but is not limited to the examples.

EXAMPLE 1

10 g of unmercerized cotton knitted goods are put in a path at pH 7which is prepared by adding 0.2 g of the reactive azo dye in free formrepresented by the following formula: ##STR21## 16 g of sodium sulfate,0.4 g of Na₂ HPO₄.12H₂ O as a buffer and 0.1 g of KH₂ PO₄ into 200 ml ofwater, and the bath is heated to 120° C. for 30 minutes. After dyeingfor 60 minutes at the same temperature, the goods dyed are washed withwater, soaped, washed with water and dried to give the dyed goods inclear red. The degree of exhaustion of the present dye is veryexcellent, and the color of dyed goods obtained is extreme density. Eachof their light fastness, fastness to chlorine and fastness to lightperspiration is fine.

Further, the reactive azo dye used in the present example can beprepared by the following procedure: The monoazo compound represented bythe following formula: ##STR22## can be prepared by the usualdiazotization and coupling of 30.3 g of 2-naphthylamine-4,8-disulfonicacid with 17.3 g of 1-aminobenzene-2-sulfonic acid. On the other hand,after condensing of 23.9 g of 2-amino-5-hydroxynaphthalene-7-sulfonicacid with 18.5 g of cyanuric chloride at 5° C. below, the compoundobtained is further condensed with 28.1 g of sulfonic acid ester of4-(β-hydroxyethyl)sulfonylaniline at 30° to 35° C. to prepare thecompound represented by the following formula: ##STR23## and then tothis reaction solution, the diazo solution prepared from the monoazocompound stated above by the usual diazotization is added. Aftercoupling, the reaction mixture is salted out with potassium chloride toobtain the reactive disazo dye stated above.

EXAMPLE 2

10 g of undyed silk cotton knitted goods are put in a bath which isprepared by adding 0.2 g of reactive azo dye in free form represented bythe following formula: ##STR24## 16 g of sodium sulfate, 0.5 g of Na₂HPO₄.12H₂ O as a buffer and 0.02 g of KH₂ PO₄ into 200 ml of water, thebath is heated to 130° C. for 30 minutes. After dyeing for 30 minutes atthe same temperature, the goods dyed are washed with water, soaped,washed with water and dried to give the dyed goods in deep blue. The pHof the bath is maintained at 8 from the beginning to the end of dyeing.The color of the dyed goods is extreme density, and each of their lightfastness, fastness to chlorine and fastness to light perspiration isfine.

Further, the reactive azo dye used in the present example can beprepared by the following procedure: The monoazo compound represented bythe following formula: ##STR25## can be prepared by the usualdiazotization and coupling of 25.3 g of aniline-2,5-disulfonic acid with13.7 g of 2-methoxy-5-methylaniline. On the other hand, after condensingof 23.9 g of 2-amino-5-hydroxynaphthalene-7-sulfonic acid with 18.5 g ofcyanuric chloride at 5° C. below, the compound obtained is furthercondensed with 28.1 g of sulfonic acid ester of3-(β-hydroxyethyl)sulfonylaniline at 30° to 35° C. to prepare thecompound represented by the following formula: ##STR26## and then tothis reaction solution, the diazo solution prepared from the monoazocompound stated above by the usual diazotization is added. Aftercoupling, the reaction mixture is dried with spray to give the reactivedisazo dye used in the present example.

EXAMPLE 3

10 g of mixed fiber of polyester with cotton (50:50) are put in a bathwhich is prepared by adding 0.2 g of the reactive dye in free formrepresented by the following formula: ##STR27## 0.2 g of the monoazo dyerepresented by the following formula: ##STR28## 12 g of sodium sulfate,0.4 g of Na₂ HPO₄.12H₂ O as a buffer and 0.1 g of KH₂ PO₄ into 200 ml ofwater, the bath is heated to 130° C. for 30 minutes. After dyeing for 60minutes at the same temperature, the goods dyed are washed with water,soaped, washed with water and dried to give the dyed goods in bluehaving a fine color equality. The pH of the bath is maintained at 8 fromthe beginning to the end of dyeing. Their exhaustibility is very fine,and the color of the dyed goods is extreme density. Each of their lightfastness, fastness to chlorine and fastness to light perspiration isfine.

Still more, the reactive disazo dye used in the present example can beprepared by the following procedure: The monoazo compound represented bythe following formula: ##STR29## can be prepared by the usualdiazotization and coupling of 38.3 g of2-naphthylamine-3,6,8-trisulfonic acid with 13.7 g of2-methoxy-5-methylaniline. On the other hand, after condensing of 31.9 gof 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid with 18.5 g ofcyanuric chloride at 5° C. below, the compound obtained is furthercondensed with 28.1 g of sulfonic acid ester of3-(β-hydroxyethyl)sulfonylaniline to prepare the compound represented bythe following formula: ##STR30## and then to this reaction solution,diazo solution prepared from the monoazo compound stated above by theusual diazotization is added. After coupling, the reaction mixture issalted out with potassium chloride to obtain the reactive dye statedabove.

EXAMPLE 4

By a similar method to Example 1 cottons are dyed with reactive disazodyes represented by the general formula (I), and results obtained areshown in Table 1.

    TABLE 1      ##STR31##      [I]               No.      ##STR32##      ##STR33##      ##STR34##      Z.sup.1      ##STR35##      color of cotton (water)λmax (nm)         4-1      ##STR36##      ##STR37##      ##STR38##      Cl      ##STR39##      violet 564  4-2      ##STR40##      ##STR41##      ##STR42##      Cl      ##STR43##      reddish blue 575  4-3      ##STR44##      ##STR45##      ##STR46##      ##STR47##      ##STR48##      reddish violet 535  4-4      ##STR49##      ##STR50##      ##STR51##      Cl      ##STR52##      blue 590  4-5      ##STR53##      ##STR54##      ##STR55##      F      ##STR56##      violet 560  4-6      ##STR57##      ##STR58##      ##STR59##      NH.sub.2      ##STR60##      violet 552  4-7      ##STR61##      ##STR62##      ##STR63##      NHCH.sub.2 CH.sub.2 SO.sub.3      H     ##STR64##      bluish red 523  4-8      ##STR65##      ##STR66##      ##STR67##      NHCH.sub.2      COOH     ##STR68##      red 520  4-9      ##STR69##      ##STR70##      ##STR71##      NH.sub.2      ##STR72##      violet 561      4-10     ##STR73##      ##STR74##      ##STR75##      Cl      ##STR76##      violet 561      4-11     ##STR77##      ##STR78##      ##STR79##      OCH.sub.3      ##STR80##      blue 590      4-12     ##STR81##      ##STR82##      ##STR83##      ##STR84##      ##STR85##      violet 563      4-13     ##STR86##      ##STR87##      ##STR88##      F      ##STR89##       bluish red 526      4-14     ##STR90##      ##STR91##      ##STR92##      Cl      ##STR93##      blue 578      4-15     ##STR94##      ##STR95##      ##STR96##      NHC.sub.2 H.sub.4      OH     ##STR97##      bluish red 525      4-16     ##STR98##      ##STR99##      ##STR100##      NHC.sub.2 H.sub.4      CH     ##STR101##      violet 565      4-17     ##STR102##      ##STR103##      ##STR104##      ##STR105##      ##STR106##      bluish red 524      4-18     ##STR107##      ##STR108##      ##STR109##      ##STR110##      ##STR111##      bluish red 534      4-19     ##STR112##      ##STR113##      ##STR114##      ##STR115##      ##STR116##      blue 585      4-20     ##STR117##      ##STR118##      ##STR119##      ##STR120##      ##STR121##      violet 560      4-21     ##STR122##      ##STR123##      ##STR124##      ##STR125##      ##STR126##      blue 588      4-22     ##STR127##      ##STR128##      ##STR129##      ##STR130##      ##STR131##      violet 560      4-23     ##STR132##      ##STR133##      ##STR134##      ##STR135##      ##STR136##      bluish red 525      4-24     ##STR137##      ##STR138##      ##STR139##      Cl      ##STR140##      blue 575

EXAMPLE 5

10 g of undyed silk cotton knitted goods are put in a bath which isprepared by adding 0.2 g of the reactive trisazo dye in free formrepresented by the following formula: ##STR141## 16 g of sodium sulfate,0.4 g of Na₂ HPO₄.12H₂ O as a buffer and 0.1 g of KH₂ PO₄ into 200 ml ofwater, the bath is heated to 120° C. for 30 minutes. After dyeing for 60minutes at the same temperature, the goods dyed are washed with water,soaped, washed with water and dried to give the dyed goods in greenishdeep blue. The degree of their exhaustion is very excellent, and thecolor of the dyed goods obtained is extreme density. Each of their lightfastness, fastness to chlorine and fastness to light perspiration isfine.

Further, the trisazo compound used in the present example can beprepared by the following procedure: The disazo compound represented bythe following formula: ##STR142## can be prepared by the usualdiazotization and coupling of 13.7 g of 2-methoxy-5-methylaniline withthe monoazo compound prepared by the usual diazotization and coupling of38.3 g of 2-naphthylamine-3,6,8-trisulfonic acid with 13.7 g of2-methoxy-5-methylaniline. On the other hand, after condensing of 31.9 gof 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid with 18.5 g ofcyanuric chloride at 5° C. below, the compound obtained is furthercondensed with 28.1 g of sulfonic acid ester of3-(β-hydroxyethyl)sulfonylaniline at 30° to 35° C. to prepare thecompound represented by the formula: ##STR143## and then to thisreaction solution, the diazo solution prepared from the disazo compoundstated above by diazotization in water-acetic acid medium is added.After coupling, the reaction mixture is salted out with potassiumchloride to obtain the trisazo compound stated above.

EXAMPLE 6

10 g of undyed silk cotton knitted goods are put in a bath which isprepared by adding 0.2 g of the trisazo compound in free formrepresented by the following formula: ##STR144## 16 g of sodium sulfate,0.5 g of Na₂ HPO₄.12H₂ O as a buffer and 0.02 g of KH₂ PO₄ into 200 mlof water, and the bath is heated to 130° C. for 30 minutes. After dyeingfor 30 minutes at the same temperature, the goods dyed are washed withwater, soaped, washed with water and dried to give the dyed goods indeep blue. The pH of the bath is maintained at 8 from the beginning tothe end of dyeing. The color of the dyed goods is extreme density andeach of their light fastness, fastness to chlorine and fastness to lightperspiration is fine.

Further, the trisazo compound used in the present example can beprepared by the following procedure: The disazo compound represented bythe following formula: ##STR145## can be prepared by the usualdiazotization and coupling of 18.0 g of 2-methoxy-5-acetylaminoanilinewith the monoazo compound prepared by the usual diazotization andcoupling of 30.3 g of 2-naphthylamine-4,8-disulfonic acid and 22.3 g of1-naphthylamine-7-sulfonic acid. On the other hand, after condensing of23.9 g of 2-amino-5-hydroxynaphthalene-7-sulfonic acid with 18.4 g ofcyanuric chloride, the compound obtained is further condensed with 28.1g of sulfonic acid ester 3-(β-hydroxyethyl)sulfonylaniline to preparethe compound represented by the following formula: ##STR146## and thenafter diazotization and coupling of this compound with the disazocompound prepared previously, the reaction mixture is dried with sprayto obtain the trisazo compound used in the present example.

EXAMPLE 7

10 g of mixed fiber of polyester with cotton (50:50) are put in a bathwhich is prepared by adding 0.2 g of the trisazo dye in free formrepresented by the following formula: ##STR147## 0.2 g of the monoazodye represented by the following formula: ##STR148## 12 g of sodiumsulfate, 0.4 g of Na₂ HPO₄.12H₂ O as a buffer and 0.1 g of KH₂ PO₄ into200 ml of water, the bath is heated to 130° C. for 30 minutes. Afterdyeing for 60 minutes at the same temperature, the goods dyed are washedwith water, soaped, washed with water and dried to give the dyed goodsin deep blue having a fine color equality. The pH of the bath ismaintained at 8 from the beginning to the end of dyeing. Theirexhaustibility is very fine, the color of the dyed goods is extremedensity. Each of their light fastness, fastness to chlorine and fastnessto light perspiration is fine.

Further, the trisazo compound used in the present example can beprepared by a similar manner to Example 6 except that 13.7 g of2-methoxy-5-methylaniline is used in place of 18.0 g of2-methoxy-5-acetylaminoaniline used in Example 6.

EXAMPLE 8

By a similar manner to Example 5 cottons are dyed with the trisazocompounds represented by the general formula (II-1), and the resultsobtained are shown in Table 2.

    TABLE 2      ##STR149##      (II-1)                No.      ##STR150##      ##STR151##      ##STR152##      ##STR153##      Z.sup.1      ##STR154##      cottoncolor of (nm)(water) λmax       8-1      ##STR155##      ##STR156##      ##STR157##      ##STR158##      Cl      ##STR159##      deep blue 566  8-2      ##STR160##      ##STR161##      ##STR162##      ##STR163##      Cl      ##STR164##      greenishdeep blue 594  8-3      ##STR165##      ##STR166##      ##STR167##      ##STR168##      Cl      ##STR169##      greenishdeep blue 586  8-4      ##STR170##      ##STR171##      ##STR172##      ##STR173##      NH.sub.2      ##STR174##      greenishdeep blue 584  8-5      ##STR175##      ##STR176##      ##STR177##      ##STR178##      NHC.sub.2 H.sub.4 SO.sub.3      H     ##STR179##      deep blue 572  8-6      ##STR180##      ##STR181##      ##STR182##      ##STR183##      Cl      ##STR184##      reddishdeep blue 561  8-7      ##STR185##      ##STR186##      ##STR187##      ##STR188##      F      ##STR189##      greenishdeep blue 586  8-8      ##STR190##      ##STR191##      ##STR192##      ##STR193##      Cl      ##STR194##      reddishdeep blue 562  8-9      ##STR195##      ##STR196##      ##STR197##      ##STR198##      NHCH.sub.2      COOH     ##STR199##      green 595      8-10     ##STR200##      ##STR201##      ##STR202##      ##STR203##      ##STR204##      ##STR205##      deep blue 565      8-11     ##STR206##      ##STR207##      ##STR208##      ##STR209##      Cl      ##STR210##      deep blue 564      8-12     ##STR211##      ##STR212##      ##STR213##      ##STR214##      Cl      ##STR215##      green 602      8-13     ##STR216##      ##STR217##      ##STR218##      ##STR219##      ##STR220##      ##STR221##      deep blue 563      8-14     ##STR222##      ##STR223##      ##STR224##      ##STR225##      NHC.sub.2 H.sub.4      OH     ##STR226##      green 601      8-15     ##STR227##      ##STR228##      ##STR229##      ##STR230##      Cl      ##STR231##      deep blue 570      8-16     ##STR232##      ##STR233##      ##STR234##      ##STR235##      Cl      ##STR236##      greenishdeep blue 588      8-17     ##STR237##      ##STR238##      ##STR239##      ##STR240##      Cl      ##STR241##      greenishdeep blue 588      8-18     ##STR242##      ##STR243##      ##STR244##      ##STR245##      Cl      ##STR246##      reddishdeep blue 560      8-19     ##STR247##      ##STR248##      ##STR249##      ##STR250##      Cl      ##STR251##      deep blue 568      8-20     ##STR252##      ##STR253##      ##STR254##      ##STR255##      Cl      ##STR256##      reddishdeep blue 566      8-21     ##STR257##      ##STR258##      ##STR259##      ##STR260##      Cl      ##STR261##      deep blue 576      8-22     ##STR262##      ##STR263##      ##STR264##      ##STR265##      Cl      ##STR266##      greenishdeep blue 582      8-23     ##STR267##      ##STR268##      ##STR269##      ##STR270##      Cl      ##STR271##      deep blue 564      8-24     ##STR272##      ##STR273##      ##STR274##      ##STR275##      Cl      ##STR276##      greenishdeep blue 578      8-25     ##STR277##      ##STR278##      ##STR279##      ##STR280##      Cl      ##STR281##      greenishdeep blue 580      8-26     ##STR282##      ##STR283##      ##STR284##      ##STR285##      Cl      ##STR286##      greenishdeep blue 585      8-27     ##STR287##      ##STR288##      ##STR289##      ##STR290##      NHC.sub.4 H.sub.9      (n)     ##STR291##      greenishdeep blue 586      8-28     ##STR292##      ##STR293##      ##STR294##      ##STR295##      ##STR296##      ##STR297##      deep blue 568      8-29     ##STR298##      ##STR299##      ##STR300##      ##STR301##      Cl      ##STR302##      deep blue 579      8-30     ##STR303##      ##STR304##      ##STR305##      ##STR306##      F      ##STR307##      deep blue 562      8-31     ##STR308##      ##STR309##      ##STR310##      ##STR311##      Cl      ##STR312##      deep blue 556      8-32     ##STR313##      ##STR314##      ##STR315##      ##STR316##      ##STR317##      ##STR318##      deep blue 552      8-33     ##STR319##      ##STR320##      ##STR321##      ##STR322##      Cl      ##STR323##      deep blue 562      8-34     ##STR324##      ##STR325##      ##STR326##      ##STR327##      Cl      ##STR328##      green 590      8-35     ##STR329##      ##STR330##      ##STR331##      ##STR332##      Cl      ##STR333##      deep blue 586      8-36     ##STR334##      ##STR335##      ##STR336##      ##STR337##      ##STR338##      ##STR339##      deep blue 560      8-37     ##STR340##      ##STR341##      ##STR342##      ##STR343##      Cl      ##STR344##      deep blue 576      8-38     ##STR345##      ##STR346##      ##STR347##      ##STR348##      NHC.sub.2 H.sub.4      CN     ##STR349##      green 593      8-39     ##STR350##      ##STR351##      ##STR352##      ##STR353##      F      ##STR354##      green 602      8-40     ##STR355##      ##STR356##      ##STR357##      ##STR358##      ##STR359##      ##STR360##      deep blue 567      8-41     ##STR361##      ##STR362##      ##STR363##      ##STR364##      Cl      ##STR365##      deep blue 562      8-42     ##STR366##      ##STR367##      ##STR368##      ##STR369##      ##STR370##      ##STR371##      reddishdeep blue 560      8-43     ##STR372##      ##STR373##      ##STR374##      ##STR375##      Cl      ##STR376##      deep blue 590      8-44     ##STR377##      ##STR378##      ##STR379##      ##STR380##      Cl      ##STR381##      reddishdeep blue 568      8-45     ##STR382##      ##STR383##      ##STR384##      ##STR385##      ##STR386##      ##STR387##      greenishdeep blue 595      8-46     ##STR388##      ##STR389##      ##STR390##      ##STR391##      NHC.sub.3 H.sub.7      (i)     ##STR392##      deep blue 585      8-47     ##STR393##      ##STR394##      ##STR395##      ##STR396##      Cl      ##STR397##      deep blue 563

EXAMPLE 9

10 g of undyed silk cotton knitted goods are put in a bath at pH 7 whichis prepared by adding 0.2 g of the trisazo dye in free form representedby the following formula: ##STR398## 16 g of sodium sulfate, 0.4 g ofNa₂ HPO₄.12H₂ O as a buffer and 0.1 g of KH₂ PO₄ into 200 ml of water,and the bath is heated to 120° C. for 30 minutes. After dyeing for 60minutes at the same temperature, the goods dyed are washed with water,soaped, washed with water and dried to give the dyed goods in greenishdeep blue. Their exhaustibility is very fine, the color of the dyedgoods is extreme density. Each of their light fastness, fastness tochlorine and fastness to light perspiration is fine.

Further, the trisazo compound used in the present example can beprepared by the following procedure: The disazo compound represented bythe following formula: ##STR399## can be prepared by the usualdiazotization and coupling of 13.7 g of 2-methoxy-5-methylaniline withthe monoazo compound prepared by the diazotization and coupling of 38.3g of 2-naphthylamine-3,6,8-trisulfonic acid with 13.7 g of2-methoxy-5-methylaniline. On the other hand, after condensing of 31.9 gof 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid with 13.5 g ofcyanuric fluoride at 0° C. below, the compound obtained is condensedwith 17.3 g of 4-aminobenzenesulfonic acid at 20° C. to prepare thecompound represented by the following formula: ##STR400## and then tothis reaction solution, the diazo solution prepared from the disazocompound stated above by the usual diazotization in water-acetic acidmedium is added. After coupling, the reaction mixture is salted out withpotassium chloride to obtain the trisazo compound stated above.

EXAMPLE 10

10 g of undyed silk cotton knitted goods are put in a bath which isprepared by adding 0.2 g of the trisazo compound in free formrepresented by the following formula: ##STR401## 16 g of sodium sulfate,0.5 g of Na₂ HPO₄.12H₂ O as a buffer and 0.02 g of KH₂ PO₄ into 200 mlof water, the bath is heated to 130° C. for 30 minutes. After dyeing for30 minutes at the same temperature, the goods dyed are washed withwater, soaped, washed with water and dried to give the dyed goods indeep blue. The pH of the bath is maintained at 8 from the beginning tothe end of dyeing. The color of the dyed goods is extreme density. Eachof their light fastness, fastness to chlorine and fastness to lightperspiration is fine.

Further, the trisazo compound used in the present example can beprepared by the following procedure: The disazo compound represented bythe following formula: ##STR402## can be prepared by the usualdiazotization and coupling of 18.0 g of 2-methoxy-5-acetylaminoanilinewith the monoazo compound prepared by the usual diazotization andcoupling of 25.3 g of aniline-2,5-disulfonic acid with 13.7 g of2-methoxy-5-methylaniline. On the other hand, after condensing of 23.9 gof 2-amino-5-hydroxynaphthalene-7-sulfonic acid with 13.5 g of cyanuricfluoride, the compound obtained is further condensed with 17.3 g of4-aminobenzenesulfonic acid to prepare the compound represented by thefollowing formula: ##STR403## and then after diazotization and couplingof this compound with the disazo compound obtained previously, thereaction mixture is dried with spray to obtain the trisazo compound usedin the present example.

EXAMPLE 11

10 g of mixed fiber of polyester with cotton (50:50) are put in a bathwhich is prepared by adding 0.2 g of the trisazo dye in free formrepresented by the following formula: ##STR404## 0.2 g of the monoazodye represented by the following formula: ##STR405## 12 g of sodiumsulfate, 0.4 g of Na₂ HPO₄.12H₂ O as a buffer and 0.1 g of KH₂ PO₄ into200 ml water, the bath is heated to 130° C. for 30 minutes. After dyeingfor 60 minutes at the same temperature, the goods dyed are washed withwater, soaped, washed with water and dried to give the dyed goods indeep blue having a fine color equality. The pH of the bath is maintainedat 8 from the beginning to the end of dyeing. Their exhaustibility isvery excellent and the color of the dyed goods is extreme density. Eachof their light fastness, fastness to chlorine and fastness to lightperspiration is fine.

Further, the trisazo compound used in the present example can beprepared by a similar manner to Example 10 except that 22.3 g of1-naphthylamine-7-sulfonic acid is used in place of 13.7 g of2-methoxy-5-methylaniline used in Example 10.

EXAMPLE 12

By a similar manner to Example 9 cottons are dyed with the trisazocompounds represented by the general formula (II-2), and the resultsobtained are shown in Table 3.

    TABLE 3      ##STR406##                No.      ##STR407##      ##STR408##      ##STR409##      ##STR410##      X Y cottoncolor of (nm)(water)λmax       12-1      ##STR411##      ##STR412##      ##STR413##      ##STR414##      Cl      ##STR415##      deep blue 571  12-2      ##STR416##      ##STR417##      ##STR418##      ##STR419##      Cl      ##STR420##      greenishdeep blue 604  12-3      ##STR421##      ##STR422##      ##STR423##      ##STR424##      Cl      ##STR425##      greenishdeep blue 591  12-4      ##STR426##      ##STR427##      ##STR428##      ##STR429##      F      ##STR430##      greenishdeep blue 594  12-5      ##STR431##      ##STR432##      ##STR433##      ##STR434##      F      ##STR435##      deep blue 582  12-6      ##STR436##      ##STR437##      ##STR438##      ##STR439##      Cl      ##STR440##      reddishdeep blue 566  12-7      ##STR441##      ##STR442##      ##STR443##      ##STR444##      F      ##STR445##      greenishdeep blue 596  12-8      ##STR446##      ##STR447##      ##STR448##      ##STR449##      Cl      ##STR450##      reddishdeep blue 567  12-9      ##STR451##      ##STR452##      ##STR453##      ##STR454##      F NH.sub.2 green 605      12-10     ##STR455##      ##STR456##      ##STR457##      ##STR458##      F NHC.sub.4 H.sub.9 (n) deep blue 575      12-11     ##STR459##      ##STR460##      ##STR461##      ##STR462##      Cl      ##STR463##      deep blue 569      12-12     ##STR464##      ##STR465##      ##STR466##      ##STR467##      Cl      ##STR468##      green 607      12-13     ##STR469##      ##STR470##      ##STR471##      ##STR472##      F      ##STR473##      deep blue 573      12-14     ##STR474##      ##STR475##      ##STR476##      ##STR477##      F NHCH.sub.2 COOH green 607      12-15     ##STR478##      ##STR479##      ##STR480##      ##STR481##      F      ##STR482##      deep blue 580      12-16     ##STR483##      ##STR484##      ##STR485##      ##STR486##      Cl      ##STR487##      greenishdeep blue 593      12-17     ##STR488##      ##STR489##      ##STR490##      ##STR491##      Cl      ##STR492##      greenishdeep blue 592      12-18     ##STR493##      ##STR494##      ##STR495##      ##STR496##      F      ##STR497##      reddishdeep blue 570      12-19     ##STR498##      ##STR499##      ##STR500##      ##STR501##      F      ##STR502##      deep blue 579       12-20     ##STR503##      ##STR504##      ##STR505##      ##STR506##      Cl NHCH.sub.2 CH.sub.2 SO.sub.3 H reddishdeep blue 571      12-21     ##STR507##      ##STR508##      ##STR509##      ##STR510##      Cl      ##STR511##      deep blue 580      12-22     ##STR512##      ##STR513##      ##STR514##      ##STR515##      Cl      ##STR516##      greenishdeep blue 586      12-23     ##STR517##      ##STR518##      ##STR519##      ##STR520##      F OCH.sub.3 deep blue 572      12-24     ##STR521##      ##STR522##      ##STR523##      ##STR524##      F      ##STR525##      greenishdeep blue 585      12-25     ##STR526##      ##STR527##      ##STR528##      ##STR529##      Cl      ##STR530##      greenishdeep blue 586      12-26     ##STR531##      ##STR532##      ##STR533##      ##STR534##      Cl      ##STR535##      greenishdeep blue 589      12-27     ##STR536##      ##STR537##      ##STR538##      ##STR539##      F      ##STR540##      greenishdeep blue 593      12-28     ##STR541##      ##STR542##      ##STR543##      ##STR544##      F      ##STR545##      deep blue 575      12-29     ##STR546##      ##STR547##      ##STR548##      ##STR549##      Cl      ##STR550##      deep blue 583      12-30     ##STR551##      ##STR552##      ##STR553##      ##STR554##      F NHC.sub.2 H.sub.4 OH deep blue 572      12-31     ##STR555##      ##STR556##      ##STR557##      ##STR558##      Cl NHC.sub.2 H.sub.4 CN deep blue 561      12-32     ##STR559##      ##STR560##      ##STR561##      ##STR562##      F      ##STR563##      deep blue 562      12-33     ##STR564##      ##STR565##      ##STR566##      ##STR567##      Cl OCH.sub.3 deep blue 571      12-34     ##STR568##      ##STR569##      ##STR570##      ##STR571##      Cl      ##STR572##      deep blue 593      12-35     ##STR573##      ##STR574##      ##STR575##      ##STR576##      F      ##STR577##      deep blue 589      12-36     ##STR578##      ##STR579##      ##STR580##      ##STR581##      F      ##STR582##      deep blue 568      12-37     ##STR583##      ##STR584##      ##STR585##      ##STR586##      Cl      ##STR587##      deep blue 581      12-38     ##STR588##      ##STR589##      ##STR590##      ##STR591##      F NHC.sub.2 H.sub.5 deep blue 598      12-39     ##STR592##      ##STR593##      ##STR594##      ##STR595##      F NH.sub.2 deep blue 612      12-40     ##STR596##      ##STR597##      ##STR598##      ##STR599##      F      ##STR600##      deep blue 575      12-41     ##STR601##      ##STR602##      ##STR603##      ##STR604##      Cl      ##STR605##      deep blue 567      12-42     ##STR606##      ##STR607##      ##STR608##      ##STR609##      F NHC.sub.2 H.sub.4 SO.sub.3      H reddishdeep blue 570

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A reactive azo dye represented by the followingformula: ##STR610## wherein M represents hydrogen or alkali metal; R¹represents hydrogen, chlorine, lower alkyl, lower alkoxy, nitro,carboxy; R² and R⁸ represent lower alkyl, lower alkoxy or sulfonic acid;R³, R⁷ and R⁹ represent hydrogen, lower alkyl, lower alkoxy, acetylaminoor sulfonic acid; R⁴ and R⁵ represent hydrogen, methyl, methoxy orsulfonic acid; R⁶ represents hydrogen, lower alkyl, lower alkoxy orsulfonic acid; Z¹ represents chlorine, fluorine, aliphatic or atomaticamino group, methoxy or phenoxy; Z² represents the same as Z¹ when Z³represents ##STR611## Z² represents chlorine or fluorine when Z³represents aliphatic amino group, aromatic amino group except ##STR612##methoxy or phenoxy; Z³ is ##STR613## aliphatic amino group, aromaticamino group except ##STR614## methoxy, or phenoxy; m represents 1, 2 or3; m' represents 2 or 3; n represents 0 or 1, and the rings A, B and Ceach represent a benzene ring or naphthalene ring, wherein the aliphaticand aromatic amino residue represented by Z¹, Z² and Z³ are --NH₂,alkylamino having 1 to 4 carbon atoms, ethanol-amino, β-cyanoethylamino,β-sulfoethylamino, --NHCH₂ COOH, anilino or anilino substituted withsulfo, chlorine, lower alkyl, lower alkoxy, nitro or carboxyl.
 2. Thereactive azo dye as claimed in claim 1 represented by formula:##STR615## wherein R¹, R², R³, R⁴, R⁵, M, m, n and Z¹ have the samemeanings as defined in claim
 1. 3. The reactive azo dye as claimed inclaim 1 represented by formula: ##STR616## wherein R⁴, R⁵, R⁶, R⁷, R⁸,R⁹, M, Z¹, m' and n have the same meanings as defined in claim
 1. 4. Thereactive azo dye as claimed in claim 1 represented by formula:##STR617## wherein X represents chlorine or fluorine; Y is aliphaticamino group, aromatic amino group except ##STR618## methoxy or phenoxy;and R⁶, R⁷, R⁸, R⁹, M, m' and n have the same meanings as defined inclaim
 1. 5. The reactive azo dye as claimed in claim 1, wherein saidlower alkyl and alkoxy represented by R¹, R³, R⁶, R⁷, R⁸ and R⁹ is alkylor alkoxy having 1 to 4 carbon atoms.
 6. The reactive azo dye as claimedin claim 1, wherein said alkali metal represented by M is sodium orpotassium.